S-benzylthiouronium dinitrophenates



Patented June 8, 1954 V UNITED STATES PATENT OFFICE S-BENZYLTHIOURONIUM DINITRO- PHENATES W E Craig and Chien-Pen Lo, Philadelphia, Pa.,

assignors to Rohm & Haas Company, Philadelphia, Pa., a corporation of Delaware No Drawing. Application February 13, 1953, Serial No. 336,881

6 Claims. (Cl. 260-3095) 1 2 This invention concerns S-benzylthiouronium recrystallized from water. It then melts at 120- dinitrophenates of the structure 122 C. and contains 8.6% of sulfur and 15.4% of X nitrogen (theory 8.8% and 15.4%, respectively),

NH NO: thus corresponding in composition to S-benzyl- S 5 thiouronium 4,6-dinitro-o-cresolate.

I This compound in standard toxicity tests gives R N Y R 02 a kill of aphids of 94%, using a spray with a wherein each R is hydrogen, or an alkyl group, 131600 g a 6 or the two Rs together form an ethylene chain, glves 0 y ugs an l X and Y represent hydrogen or chlorine and 10 oi red spideis. Against beanbeetle larvae it B. represents an alkyl group of not over eight g-lves a km of 89%-when apphed at a 05% dilucarbon atoms a cyciohexyl group or chlorine tion. It is not toxic to tomato or bean plants at These compounds are effective fungicidal and/0r useful dlmtmns' This is in surprising contrast to the S-benzylgzg agents fish polsons and/or mollusca" thiouronium picric acid salt, which gives no con- While picric acid salts of a number of thiogiig gigg igggigzigggg gggigfii and Is very uronium compounds have been made for purposes of isolation and/or identification, these x p 2 salts are lacking in the properties which render A mixture of 133 parts f useful the compound of this invention 2O thiourea, 138 parts of benzyl chloride, and 500 thermore, the picric acid salts are two phytocidal parts of ethanol is heated under flu f f to permit their application to green plantshours. The mixture is concentrated under re- The compounds of this invention are prepared duced pressure, the dibutyi s benzylby mixing a thiouronium halide and an alkali metal salt of a dinitrophenol in an inert organic solvent, efiecting reaction, and separating alkali A portion of 23 parts of this oil is dissolved in metal halide and thiouronium dinitrophenate, methanol and thereto is added a soiuticn of thus sodium 2capryl-4,6-dinitrophenate in methanol. R-NH Water is added and an oil separates. This is taken up in benzene, washed with water, and O SB'HX (NOmR CGHQOM dried. The benzene is evaporated to leave a dark red oil, which corresponds in composition to N,N'-dibutyl-S-benzylthiouronium 2-capryl-4,6-

OSB:-HOC6H2R(NO2)2 MX dinitrophenata R-N At a dilution of 1:400 in a spray this comvhere B represents a nucleus pOllIld glVeS a 0f red Spiders; at

The reaction is effected between 25 and 125 c. a kill; and at 1:1600. a 99% kill. A wetin a solvent such as ethylene dichloride, toluene, table P w at one Pound 100 gallons gave benzene, ethanol, isopropanol, aqueous methanol, 3 K111 of red spider, while at e1ght pounds or acetone, etc. The product and salt are sepaper 100 gallons commund m Wettable rated, as by filtering, washing with water, or der gave a 73% km agamst army Wormprecipitating with water from water miscible f 9 N;N'-dibutyl-s-lqenzvlihiourea and Solvents. picrlc acid is highly phytotoxic to green plants.

Typical preparations are described in the fol- Emmple 3 g g fi examples n which parts are In the same way there are reacted 237 parts Example 1 of S-2-chlorobenzylthiouronium chloride and 296 parts of a solution of 198 parts of 2,4-dinitro-o- A solution is prepared from 20 parts of 4,6- cresol solubilized with about an equivalent of dinitro-o-cresol, 4 parts of sodium hydroxide, 100 caustic soda solution. The product formed is parts of methanol, and 100 parts of water. To S-(Z chlorobenzyDthiouronium 4,6 dinitro-othis is added a solution of 20.3 parts of S-benzylcresolate.

thiouronium chloride in parts of ethanol. The This compound tested against aphids in a spray mixture is stirred for an hour and diluted with gives a kill of 72% at a dilution of 1:1600. At

water. A solid separates. It is filtered off and 55 a dilution of 1:1200 it gives a kill of against thiouronium chloride is collected as an orange 3 red spider, Against bean beetle larvae it gives a kill of 92% when used at of 90% when used at 0.25%, and of 73% when used at 0.125%. It is not phytotoxic to tomatoes or beans.

The comparable picric acid salt is ineffective and highly phytotoxic.

Example 4 In the same way there are reacted equivalent weights of S-benzylthiouronium chloride and sodium 2-capryl-4,6-dinitrophenate to form 5- benzylthiouronimn 2-capryl-4,6-dinitrophenate. In the Feet-Grady test this compound at 5% gives a knock-down of 97% and a kill of +22 compared to the Ofiicial Test Insecticide. At a dilution of 1 :1600 in a spray this compound gives a kill of aphids of 97%. At a dilution of 1:1200 in a spray this compound gives a kill of 100% of red spider. In tests against bean beetle larvae this compound at 1% gives a kill of 100%, at 0.5% of 93%, at 0.25% of 89%, and at 0.125% of 83%. It is not phytotoxic to beans or tomatoes.

Example 5 In the same way equivalent weights of S-(ISA- dichlorobenzyl)thiouronium chloride and sodium 2 capryl 4,6 dinitrophenate are reacted in ethanol and water to form S-(3,4-dichlorobenzyl) thiouronium 2-capryl-4,6-dinitrophenate. This compound was made into a 5% dust, which Was applied against aphids with a kill of 98%. A 2% dust gave a kill of 92%, while a 1% dust gave a kill of 79% against aphids. These dusts were also applied to red spiders, kills of 100% being obtained at 5% and 2% and of 99% at 1%. In a spray at 1:400 this compound gave a kill of 98% against red spider and 93% against aphids.

Example 6 In the same way N,N-dibutylthiourea is reacted with benzyl chloride to form S-benzyl- N,N-dibutylthiouronium chloride. This is reacted with sodium 2-cyclohexyl-4,6-dinitrophenate. The S-benzyldibutylthiouronium 2- cyclohexyldinitrophenate thus prepared gives a 100% kill of red spiders when a 1:400 spray is used with a 99% kill at 1:800 and at 121000. A wettable powder applied at a dilution giving one pound of this compound per 100 gallons of water gives a 98% kill of red spider. worm this compound gives a 73% kill when applied in a spray at 1:800.- On bean plants this compound exhibits slight toxicity. In standard fungitoxicity-tests this compound at 0.005% inhibits completely germination of spores of Against army 4 Sclerotim'a fructicola and at 0.1% spores of Macrosporium sarcinaeforme.

In place of the N-butyl groups there may be used other alkyl groups, particularly those of not over four carbon atoms each. These compounds all have marked pesticidal action without development of troublesome phytotoxicity.

Example 7 In the same way N,N-ethylenethiourea is reacted with 3,4-dichlorobenzyl chloride to form N,N'-ethylenethiouronium chloride, which is in turn reacted with sodium 2-capryl-l,6-dinitrophenate to give S-3,4-dichlorobenzyl-N,N-ethylenethiouronium 2-capryl-fi-dinitrophenate.

This compound in a spray gives kills of aphids as follows: at 1:400, 92%; at 1:800, 87%; at 1:160(), 92%; and at 1:3200, 83%. At 1:400 it gives a kill of 82% against milkweed bug. At eight pounds per 100 gallons it gives a kill of 100% against army worm. While this compound shows some evidence of being phytotoxic to beans, it is not phytotoxic to young tomato plants.

We claim:

1. As chemical substances, compounds of the structure wherein the R groups represent individually a member of the class consisting of hydrogen and alkyl of not over four carbon atoms and represent when taken together an N,N'-ethylene group, It represents a member of the class consisting of alkyl groups of not over eight carbon atoms, the cyclohexyl group, and chlorine, X and Y represent members of the class consisting of hydrogen and chlorine.

2. As a chemical compound, S-benzylthiouronium 4,6-dinitro-o-cresolate.

3. As a chemical compound, S-chlorobenzylthiouronium ZA-dinitro-o-cresolate.

4. As a chemical compound, S-benzylthiouronium 2-capryl-4,6-dinitrophenate.

5. As a chemical compound, S-(3,4-dichlorobenzyDthiouronium 2 capryl 4,6 dinitrophenate.

6. As a chemical compound, S-(3,4-dichloro)- benzyl-YZN-ethylenethiouronium 2-capryl4,6- dinitrophenate.

No references cited. 

1. AS CHEMICAL SUBSTANCES, COMPOUNDS OF THE STRUCTURE 